| 摘要: | 本篇論文主軸以環境中重要之空氣污染物─揮發性有機化合物作為主軸，因應不同法規目的性區分為有害空氣污染物(HAPs)與光化臭氧前驅物(PAMS)兩大監測技術呈現結果。第一部分是針對工業區周邊敏感受體點之HAPs實場監測；第二部分為探討金屬有機骨架 材料(MOF)之氣體吸脫附特性應用於氣相層析(GC)監測技術。
針對第一部分，於高雄仁大工業區進行有害空氣污染物現地監測與溯源分析，利用熱脫附氣相層析質譜儀(TD-GC/MS)進行線上連續監測空氣中86項HAPs，近7週的連續監測結果顯示含氯有機物氯烷類(一氯-四氯甲烷)、氯乙烯、1,2-二氯乙烷；丁二烯、丙烯腈、正己烷、醋酸乙烯酯等，為該區顯著毒性有機物。藉由比對去年同期監測數據之最大值與平均值，除了醋酸乙烯酯呈現上升趨勢之外，多數物質已明顯下降。藉由與光化學監測站比對結果，共同項目呈現高度相關(r > 0.92)，驗證了TD-GC/MS線上連續監測方法之可靠性。
第二部分為探討MOF材料應用於氣體吸脫附特性應用於TD-GC/MS技術，挑選MOF材料中較為疏水之UiO-66、耐高溫UiO-66與UiO-67作為54項C2-C11 PAMS目標物之吸脫附測試，並與商業化多重床碳吸附劑探討吸附能力。研究結果顯示單一材料UiO-66、耐高溫UiO-66與UiO-67即可吸附範圍涵蓋C3-C11的碳氫化合物物種，檢量線線性良好 (R2> 0.995)。 UiO-66、耐高溫UiO-66與多重床碳吸附劑在單位碳感度分析結果顯示彼此之吸脫附能力相近；UiO-67則在中、高碳物種吸附量較多，而輕、極高碳物種則吸附量較少。接續探討耐高溫UiO-66與UiO-67在多次吸、脫附與反覆(>100 次)升降溫後材料結構完整性測試；X光繞射儀測量結果顯示耐高溫UiO-66在高溫後晶體維持完整，而UiO-67則結晶度下降，特性峰型劣化。
最後將耐高溫UiO-66與UiO-67應用於環境周界氣體吸附測試，搭配每日中濃度與空白測試查核，連續測試五天之結果查核回收率為81%-111%之間，相對標準偏差(RSD) < 3%，符合NIEA A505.12B標準方法查核允收標準(回收率≦±25%)，顯示單一成分吸附劑耐高溫UiO-66和UiO-67適合當作有機物質吸附材料。;The central focus of this paper revolves around volatile organic compounds (VOCs), which are significant air pollutants in the environment. These compounds are further categorized into hazardous air pollutants (HAPs) and photochemical ozone precursors (PAMS) based on their characteristics. The first section of the paper concentrates on monitoring hazardous air pollutants at sensitive receptor sites in the vicinity of industrial areas. Thermal desorption gas chromatography-mass spectrometry (TD-GC/MS) is employed to conduct online continuous monitoring of 86 toxic organic substances. The monitoring results reveal that toxic organics such as vinyl chloride, 1,2-dichloroethane, butadiene, acrylonitrile, n-hexane, vinyl acetate, etc., are prominent in the Renda Industrial Zone. A comparison of the current and previous year′s monitoring data indicates a decrease for most target compounds, except for vinyl acetate, which displays increased concentrations. When compared with data from the PAMS stations, there is a strong correlation observed among common compounds (r >0.92), validating the robustness of the online continuous monitoring method.
The second part of my research explores the gas adsorption characteristics of metal-organic-framework (MOF) materials. Specifically, the relatively hydrophobic UiO-66, heat-resistant UiO-66, and UiO-67 among MOF materials are chosen as adsorbents to evaluate their adsorption capacity for the 54 PAMS species and to compare with commercial carbon adsorbents. Our findings demonstrate that these three materials can effectively adsorb hydrocarbon species ranging from C3 to C11. The calibration curve exhibits good linearity (R2 > 0.995), and the adsorption capacity of these MOF materials is comparable to that of the multi-bed carbon adsorbents. Additionally, the per-carbon response results indicate that the adsorption capacity of UiO-66 and heat-resistant UiO-66 is similar to that of the multi-bed carbon adsorbents, while UiO-67 exhibits slightly higher adsorption capacity for medium and heavy carbon species but lower adsorption capacity for smaller and extremely heavy carbon species. The study further investigates the structural differences between heat-resistant UiO-66 and UiO-67 after repeated cryogenic adsorption and thermal desorption using X-ray diffractometry. The results reveal that heat-resistant UiO-66 maintains its crystallinity under heating conditions, while the crystallinity of UiO-67 collapses to some degree, accompanied by poor peak shape as shown by the X-ray result.
Finally, the heat-resistant UiO-66 and UiO-67 are subjected to continuous heating cycles (>100) of thermal desorption and analysis along with calibration and blank tests. The recovery rate falls within 81%-111%, and the relative standard deviation (RSD) is less than 3%, complying with the NIEA A505.12B standard method acceptance criteria (recovery≦±25%). This demonstrates that adsorbents incorporating heat-resistant UiO-66 and UiO-67 are ideal for the application of thermal desorption of ambient-level VOCs. |
